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United States Patent |
5,741,437
|
Arbogast
,   et al.
|
April 21, 1998
|
N-alkyl ammonium acetonitrile bleach activators
Abstract
Bleaching compositions are provided that comprise a nitrile containing
compound that has the nitrile bonded to a quaternary nitrogen through a
methylene unit (where one or both of the normal hydrogens can be
substituted), and two of the quaternary nitrogen bonds are part of a
saturated ring. This saturated ring contains from two to eight atoms in
addition to the quaternary nitrogen. A source of active oxygen will react
with the nitrile for bleaching applications. Particularly preferred
nitrile containing compounds are N-alkyl morpholinium acetonitrile salts.
Inventors:
|
Arbogast; James W. (Dublin, CA);
Deline; James E. (Livermore, CA);
Foland; Lafayette D. (Dublin, CA);
Kaaret; Thomas W. (Alamo, CA);
Klotter; Kevin A. (Livermore, CA);
Petrin; Michael J. (Antioch, CA);
Smith; William L. (Pleasanton, CA);
Zielske; Alfred G. (Pleasanton, CA)
|
Assignee:
|
The Clorox Company (Oakland, CA)
|
Appl. No.:
|
720602 |
Filed:
|
October 1, 1996 |
Current U.S. Class: |
252/186.39; 252/186.38; 510/312 |
Intern'l Class: |
C09K 003/00; C01B 015/10; C11D 003/39; C11D 003/395 |
Field of Search: |
544/86,163,402
546/246
252/186.38,186.39
510/312
|
References Cited
U.S. Patent Documents
2425693 | Aug., 1947 | Cook et al. | 558/459.
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2489950 | Nov., 1949 | Blicke | 546/205.
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2625547 | Jan., 1953 | Lawson et al. | 544/171.
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2774758 | Dec., 1956 | Yanko | 544/163.
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2848450 | Aug., 1958 | Rudner et al. | 544/164.
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2851458 | Sep., 1958 | Billingmurst | 544/163.
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2868786 | Jan., 1959 | Siemer et al. | 544/171.
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3532735 | Oct., 1970 | Morgan | 558/455.
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3689470 | Sep., 1972 | Shachat et al. | 526/312.
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3772275 | Nov., 1973 | Hernestam et al. | 544/165.
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3780092 | Dec., 1973 | Samour et al. | 560/222.
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3873583 | Mar., 1975 | Walz et al. | 554/103.
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3882035 | May., 1975 | Loffelman et al. | 510/313.
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4086175 | Apr., 1978 | Kravetz et al. | 510/314.
|
4134889 | Jan., 1979 | Distler et al. | 546/246.
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4164511 | Aug., 1979 | Distler et al. | 558/346.
|
4199466 | Apr., 1980 | Benson, Jr. | 510/314.
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4215003 | Jul., 1980 | Finley et al. | 8/111.
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4328226 | May., 1982 | Witek et al. | 424/248.
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4342872 | Aug., 1982 | Grier et al. | 546/186.
|
4397757 | Aug., 1983 | Bright et al. | 252/186.
|
4551526 | Nov., 1985 | Mai et al. | 544/163.
|
4737498 | Apr., 1988 | Banasiak et al. | 514/234.
|
4751015 | Jun., 1988 | Humphreys et al. | 252/186.
|
4904406 | Feb., 1990 | Darwent et al. | 252/186.
|
4915863 | Apr., 1990 | Aoyagi et al. | 510/376.
|
4921631 | May., 1990 | Gradwell et al. | 252/186.
|
4978770 | Dec., 1990 | Aoyagi et al. | 558/455.
|
5093022 | Mar., 1992 | Sotoya et al. | 252/186.
|
5106528 | Apr., 1992 | Francis et al. | 252/186.
|
5236616 | Aug., 1993 | Oakes et al. | 252/186.
|
5281361 | Jan., 1994 | Adams et al. | 252/186.
|
5330677 | Jul., 1994 | Sotoya et al. | 252/186.
|
5399746 | Mar., 1995 | Steiger et al. | 560/251.
|
5405412 | Apr., 1995 | Willey et al. | 8/111.
|
5460747 | Oct., 1995 | Gosselink et al. | 252/186.
|
5591378 | Jan., 1997 | Deline et al. | 252/186.
|
Foreign Patent Documents |
883075582 | Aug., 1988 | EP.
| |
A20303520 | Aug., 1988 | EP.
| |
912012606 | May., 1991 | EP.
| |
912011707 | May., 1991 | EP.
| |
P25035829 | Jan., 1975 | DE.
| |
P25557691 | Dec., 1975 | DE.
| |
P26204455 | May., 1976 | DE.
| |
62-225871 | Sep., 1987 | JP.
| |
63-167157 | Jul., 1988 | JP.
| |
1230773 | Sep., 1989 | JP.
| |
6136391 | Oct., 1992 | JP.
| |
Other References
Hart et al., "Some New Quaternary-Substituted Alkyl Morpholinium Chlorides
and Pyrrolidinium Alkyl Sulfates," Journal of Organic Chemistry, 22:1
(Mar. 5, 1957), pp. 86-88.
|
Primary Examiner: Anthony; Joseph D.
Attorney, Agent or Firm: Majestic, Parsons,Siebert & Hsue
Parent Case Text
This is a division of application Ser. No. 08/475,292, filed Jun. 7, 1995
now allowed.
Claims
It is claimed:
1. A method of bleaching an article comprising:
providing a nitrile, the nitrile including at least one moiety reactive
with peroxygen and having the structure
##STR11##
where n is an integer of 0 to about 8 and Y is a counterion; and, reacting
the nitrile in an alkaline solution, the alkaline solution having
peroxygen therein, to form a bleaching agent;
wherein the said formed bleaching agent is contacted with an article to be
bleached.
2. The method as in claim 1 wherein the alkaline solution is at a pH of
between about 8 to about 11.
3. The method as in claim 2 wherein the alkalinity of the solution is from
a detergent source.
4. A bleaching composition comprising:
a nitrile having either the Formula IIIA or IIIB structure
##STR12##
wherein B is a saturated ring formed by a plurality of atoms in addition
to the N.sub.1 atom, the saturated ring atoms optionally. including one or
more of O, S and N atoms, the substituent R.sub.1 bound to the N.sub.1
atom of the Formula IIIA structure is (a) a C.sub.1-24 alkyl or
alkoxylated alkyl where the alkoxy is C.sub.2-4, (b) a C.sub.4-24
cycloalkyl, (c) a C.sub.7-24 alkaryl, (d) a repeating or nonrepeating
alkoxy or alkoxylated alcohol, where the alkoxy unit is C.sub.2-4, or (e)
another --CR.sub.2 R.sub.3 C.tbd.N, in Formula IIIA at least one of the
R.sub.2 and R.sub.3 substituents is H and the other of R.sub.2 and R.sub.3
is H, a C.sub.1-24 alkyl, cycloalkyl, or alkaryl, or a repeating or
nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is
C.sub.2-4, and in Formula IIIB at least one of the R.sub.2 and R.sub.3 and
at least one of the R.sub.2 ' and R.sub.3 ' substituents are H and the
other of R.sub.2 and R.sub.3 and of R.sub.2 ' and R.sub.3 ' are H, a
C.sub.1-24 alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating
alkoxyl or alkoxylated alcohol where the alkoxy unit is C.sub.2-4, the
R.sub.4 linking group includes a polyoxyalkylene group with 1 to 24
oxyalkylene units, where one or more oxygen atoms may be replaced by a
sulfur atom, or an alkylene group with 1 to 24 carbons, and Y is at least
one counterion; and,
a peroxygen releasing source.
5. The bleaching composition as in claim 4 further including an acidic
buffering agent.
6. The bleaching composition as in claim 4 wherein the source of active
oxygen includes an alkali or alkaline earth metal salt of percarbonate,
perborate, persilicate, a hydrogen peroxide adduct, or hydrogen peroxide.
7. The bleaching composition as in claim 4 further including a chelating
agent.
8. The bleaching composition as in claim 4 wherein the nitrile has the
structure
##STR13##
where Y is at least one counterion and n is 0 to 23.
9. The bleaching composition as in claim 4 further including one or more
cleaning adjuvants.
10. The bleaching composition as in claim 4 further including a buffering
agent sufficient to maintain an alkaline pH when the composition is in an
aqueous solution.
11. The bleaching composition as in claim 10 wherein the alkaline buffering
agent is separated from the nitrile until use.
12. The bleaching composition as in claim 4 wherein B is a saturated ring
formed by four carbon atoms and one oxygen atom in addition to the N.sub.1
atom.
13. The bleaching composition as in claim 4 wherein B is a saturated ring
formed by four carbon atoms and a N.sub.2 atom in addition to the N.sub.1
atom, with N.sub.2 being a secondary amine, a tertiary amine having the
substituent --CR.sub.5 R.sub.6 CN, or a quaternary amine having the
substituents --R.sub.5 and --CR.sub.5 R.sub.6 CN, and wherein R.sub.5 and
R.sub.6 may each be a H or C.sub.1-6 alkyl.
14. The bleaching composition as in claim 4, 12 or 13 wherein the alkylene
of the linking group includes an alkylene ether or an alkylene thioether.
15. The bleaching composition as in claim 14 wherein the linking group
includes --(CH.sub.2).sub.k, (CH.sub.2 CH.sub.2 O).sub.k --(CH.sub.2
CH.sub.2)--, or
##STR14##
where k=1 to 24.
16. A substantially shelf-stable composition, useful in cleaning,
comprising:
a nitrile having either the Formula IIIA or IIIB structure
##STR15##
wherein B is a saturated ring formed by a plurality of atoms in addition
to the N.sub.1 atom, the saturated ring atoms optionally including one or
more of O, S and N atoms, the substituent R.sub.1 bound to the N.sub.1
atom of the Formula IIIA structure is (a) a C.sub.1-24 alkyl or
alkoxylated alkyl where the alkoxy is C.sub.2-4, (b) a C.sub.4-24
cycloalkyl, (c) a C.sub.7-24 alkaryl, (d) a repeating or nonrepeating
alkoxy or alkoxylated alcohol, where the alkoxy unit is C.sub.2-4, or (e)
another --CR.sub.2 R.sub.3 C.tbd.N, in Formula IIIA at least one of the
R.sub.2 and R.sub.3 substituents is H and the other of R.sub.2 and R.sub.3
is H, a C.sub.1-24 alkyl, cycloalkyl, or alkaryl, or a repeating or
nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is
C.sub.2-4, and in Formula IIIB at least one of the R.sub.2 and R.sub.3 and
at least one of the R.sub.2 ' and R.sub.3 ' substituents are H and the
other of R.sub.2 and R.sub.3 and of R.sub.2 ' and R.sub.3 ' are H, a
C.sub.1-24 alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating
alkoxyl or alkoxylated alcohol where the alkoxy unit is C.sub.2-4, the
R.sub.4 linking group includes a polyoxyalkylene group with 1 to 24
oxyalkylene units, where one or more oxygen atoms may be replaced by a
sulfur atom, or an alkylene group with 1 to 24 carbons, and Y is at least
one counterion;
a peroxygen releasing source, the peroxygen releasing source to nitrile
being in a molar ratio of about 0.1:1 to 100:1; and
a buffering agent.
17. The composition as in claim 16 wherein the composition is in solution,
and the buffering agent is an acidic buffering agent.
18. A bleaching composition comprising:
a nitrile having the structure of Formula IA or Formula IB
##STR16##
wherein A is a saturated ring formed by a plurality of atoms in addition
to the N.sub.1 atom, the saturated ring atoms including at least one
carbon atom and at least one or more of O, S and N atoms, the substituent
R.sub.1 bound to the N.sub.1 atom of the Formula IA structure is (a) a
C.sub.1-8 alkyl or alkoxylated alkyl where the alkoxy is C.sub.2-4 (b) a
C.sub.4-24 cycloalkyl, (c) a C.sub.7-24 alkaryl, (d) a repeating or
nonrepeating alkoxy or alkoxylated alcohol, where the alkoxy unit is
C.sub.2-4, or (e) another --CR.sub.2 R.sub.3 C.tbd.N, in Formula IA at
least one of the R.sub.2 and R.sub.3 substituents is H and the other of
R.sub.2 and R.sub.3 is H, a C.sub.1-24 alkyl, cycloalkyl, or alkaryl, or a
repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy
unit is C.sub.2-4, and in Formula IB at least one of the R.sub.2 and
R.sub.3 and at least one of the R.sub.2 ' and R.sub.3 ' substituents are H
and the other of R.sub.2 and R.sub.3 and of R.sub.2 ' and R.sub.3 ' are H,
a C.sub.1-24 alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating
alkoxyl or alkoxylated alcohol where the alkoxy unit is C.sub.2-4, the
R.sub.4 linking group includes a polyoxyalkylene group with 1 to 24
oxyalkylene units, where one or more oxygen atoms may be replaced by a
sulfur atom, or an alkylene group with 1 to 24 carbons, and Y is at least
one counterion; and,
a peroxide releasing source.
19. The bleaching compound as in claim 18 wherein the Formula IA compound
is a N-methylmorpholinium acetonitrile salt.
20. The bleaching compound as in claim 18 wherein the counterion is
selected from the group consisting of bromide, nitrate, and alkyl sulfate.
21. The bleaching compound as in claim 20 wherein A is a saturated ring
formed by four carbon atoms and one oxygen atom in addition to the N.sub.1
atom.
22. A peroxygen bleach composition comprising:
a peroxygen activator having at least one moiety reactive with peroxygen
and having the structure
##STR17##
where n is an integer of 0 to about 8 and Y is a counterion; and, a liquid
or solid source of peroxygen.
23. The peroxygen bleach composition as in claim 22 where n is 0.
24. The peroxygen bleach composition as in claim 22 wherein the peroxygen
source is solid and further comprises sufficient of an acidic buffering
agent to shelf-stabilize the bleach.
25. The peroxygen bleach composition as in claim 22 wherein the activator
and peroxygen source react in solution to provide enhanced bleaching with
respect to the peroxygen source itself.
26. The peroxygen bleach composition as in claim 25 wherein the peroxygen
source to nitrile are in a molar ratio of about 0.1:1 to 100:1.
Description
FIELD OF THE INVENTION
The present invention generally relates to N-alkyl ammonium acetonitrile
compounds, and particularly for use as activators for hydrogen peroxide in
bleaching and cleaning applications.
BACKGROUND OF THE INVENTION
Peroxy compounds are effective bleaching agents, and compositions including
mono- or di-peroxyacid compounds are useful for industrial or home
laundering operations. For example, U,S. Pat. No. 3,996,152, issued Dec.
7, 1976, inventors Edwards et al., discloses bleaching compositions
including peroxygen compounds such as diperazelaic acid and
diperisophthalic acid.
Peroxyacids (also known as "peracids") have typically been prepared by the
reaction of carboxylic acids with hydrogen peroxide in the presence of
sulfuric acid. For example, U.S. Pat. No. 4,337,213, inventors Marynowski
et al., issued Jun. 29, 1982, discloses a method for making diperoxyacids
in which a high solids throughput may be achieved.
However, granular bleaching products containing peroxyacid compounds tend
to lose bleaching activity during storage, due to decomposition of the
peroxyacid. The relative instability of peroxyacid can present a problem
of storage stability for compositions consisting of or including
peroxyacids.
One approach to the problem of reduced bleaching activity of peroxyacid
compositions has been to include activators of peroxyacids. U.S. Pat. No.
4,283,301, inventor Diehl, issued Aug. 11, 1981, discloses bleaching
compositions including peroxygen bleaching compounds, such as sodium
perborate monohydrate or sodium perborate tetrahydrate, and activator
compounds such as isopropenyl hexanoate and hexanoyl malonic acid diethyl
ester.
U.S. Pat. No. 4,778,618, Fong et al., issued Oct. 18, 1988 provides novel
bleaching compositions comprising peracid precursors with the general
structure
##STR1##
wherein R is C.sub.1-20 linear or branched alkyl, alkylethoxylated,
cycloalkyl, aryl, substituted aryl; R' and R" are independently H,
C.sub.1-20 alkyl, aryl, C.sub.1-20 alkylaryl, substituted aryl, and
N.sup.+ R.sub.3 .sup..alpha., wherein R.sup..alpha. is C.sub.1-30 alkyl;
and where L is a leaving group which can be displaced in a peroxygen
bleaching solution by peroxide anion. U.S. Pat. Nos. 5,182,045, issued
Jan. 26, 1993, and 5,391,812, issued Feb. 21, 1995, inventors Rowland et
al. are similar, but are polyglycolates of the Fong et al. monoglycolate
precursors, or activators.
U.S. Pat. No. 4,915,863, issued Apr. 10, 1990, inventors Aoyagi et al.,
discloses compounds said to be peracid precursors that have nitrile
moieties. U.S. Pat. No. 5,236,616, issued Aug. 17, 1993, inventors Oakes
et al., discloses compounds said to be cationic peroxyacid precursors that
have nitrile moieties. These nitrile containing activators do not contain
a leaving group, such as the Fong et al. leaving groups, but instead
include a quaternary ammonium group suggested as activating the nitrile
and said, upon hydrolysis in the presence of hydrogen peroxide, to
generate a peroxy imidic acid as bleaching species. The Aoyagi et al.
activators include an aromatic ring, which tends to cause fabric
yellowing.
Thus, new peroxygen activators that do not gray or harm fabrics and that
provide superior bleaching remain desirable for laundry and household
bleaching and cleaning applications, such as laundry detergents, laundry
bleaches, hard surface cleaners, toilet bowl cleaners, automatic
dishwashing compositions, and the like.
SUMMARY OF THE INVENTION
In one aspect of the present invention, novel compounds are provided that
have the Formula I (A and B) structure:
##STR2##
In the general Formula I structure (with both A and B subparts), A is a
saturated ring formed by a plurality of atoms in addition to the N.sub.1
atom. The ring atoms include at least one carbon atom and at least one of
O, S and N atoms. R.sub.2 and R.sub.3 are each H, a C.sub.1-24 alkyl,
cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or
alkoxylated alcohol where the alkoxy unit is C.sub.2-4. "Y" is at least
one counterion.
The Formula IA structure has a R.sub.1 substituent bonded to the N.sub.1
atom. The R.sub.1 substituent includes either:
(a) a C.sub.1-24 alkyl or alkoxylated alkyl where the alkoxy is C.sub.2-4 ;
a C.sub.4-24 cycloalkyl; a C.sub.7-24 alkaryl; or a repeating or
nonrepeating alkoxy or alkoxylated alcohol, where the alkoxy unit is
C.sub.2-4 ;
or
(b) --CR.sub.2 R.sub.3 C.tbd.N where R.sub.2 and R.sub.3 are each H, a
C.sub.1-24 alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating
alkoxyl or alkoxylated alcohol where the alkoxy unit is C.sub.2-4.
The Formula IB dimer structure has R.sub.2 ' and R.sub.3 ' chosen from the
same moieties as R.sub.2 and R.sub.3 and which may be the same as R.sub.2
and R.sub.3 or be different, and has a R.sub.4 linking group bonded to the
N.sub.1 atom. The R.sub.4 substituent includes a polyoxyalkylene group
with 1 to 24 oxyalkylene units or an alkylene group with 1 to 24 carbons,
as well as thioethers.
The Formula I compounds have a quaternary nitrogen atom (N.sub.1) so at
least one appropriate counterion (Y) will be associated therewith.
The novel compounds with the Formula I structure are particularly useful
when formulated as compositions that include a source of active oxygen,
and these compositions provide excellent bleaching in alkaline solutions
without causing fabric yellowing.
Preferred embodiments of the invention include salts of N-methyl
morpholinium acetonitrile, N-butyl morpholinium acetonitrile, N-hexyl
morpholinium acetonitrile, and N-octyl morpholinium acetonitrile, which
are illustrated by Formula II (with "n" being 0 to 23 and where "Y" is the
at least one counterion).
##STR3##
A particularly preferred embodiment of the invention is an N-methyl
morpholinium acetonitrile salt (sometimes designated "MMA" where "n" of
Formula II is O) which has excellent stability, shows improved bleaching
and cleaning performance when formulated with a source of active oxygen in
alkaline wash water, and which causes no fabric graying.
In another aspect of the present invention, a bleaching composition
comprises a source of active oxygen and a nitrile having the Formula IIIA
structure:
##STR4##
In the Formula IIIA structure, B is a saturated ring formed by a plurality
of atoms in addition to the N.sub.1 atom, and the ring atoms optionally
include one or more of O, S and N atoms.
Formula IIIA is analogous to Formula I; however, the B saturated ring can
be all carbons (except for the N.sub.1 atom). As with the dimeric Formula
IB, another aspect of this invention concerns a dimeric nitrile with a B
saturated ring as just described.
In yet another aspect of this invention, a composition includes a nitrile
containing compound, the nitrile bonded to a quaternary nitrogen through a
methylene unit, two of the quaternary nitrogen bonds being part of a
saturated ring. This nitrile containing compound is preferably formulated
with a peroxide compound for bleaching applications.
Compositions of the invention are useful as or in laundry products, such as
bleaching additives, detergents, detergent boosters, detergents with
bleach, bleaches, bleaching aids, stain removers, and spot treatment
products such as stain removers, prewash and presoak laundry aids. Among
the advantages derived from compositions of the invention are improved
cleaning, stain removal, spot removal, whitening, and brightening of
treated articles without causing fabric yellowing.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Compounds of the invention include certain nitriles having the structure
illustrated by Formula I (A and B). The N.sub.1 atom of the Formula I
(both A and B subparts) compound is part of a saturated ring, illustrated
by "A" in Formula I.
##STR5##
This saturated ring of which N.sub.1 is a part has a plurality of atoms.
The saturated ring illustrated by ring "A" in Formula I has at least one
hetero atom in the saturated ring in addition to the N.sub.1, preferably
wherein the ring includes an oxygen atom, a sulfur atom, or one or two
additional nitrogen atoms.
The at least one nitrogen in the saturated ring (N.sub.1) shown in Formula
I is N-acetonitrile substituted and also quaternized. Without being bound
by theory, we believe that the electron withdrawing nature of the
quaternary nitrogen may be increased by being part of a saturated,
heterocyclic ring and may also function to improve the hydrophilic
character of the oxidant.
A substituent R.sub.1 will be bonded to the N.sub.1 atom of the Formula IA
structure and additionally a nitrile moiety (--CR.sub.2 R.sub.3 C.tbd.N)
is bonded to the N.sub.1 atom, where R.sub.2 and R.sub.3 are each H, a
C.sub.1-24 alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating
alkoxyl or alkoxylated alcohol where the alkoxy unit is C.sub.2-4. The
R.sub.1 substituent may be a C.sub.1-24 alkyl or alkoxylated alkyl where
the alkoxy is C.sub.2-24, a C.sub.4-24 cycloalkyl alkoxy or alkaryl, a
repeating or nonrepeating alkoxy or alkoxylated alcohol, where the alkoxy
unit is C.sub.2-4, and illustrative such groups are, for example,
##STR6##
where j=1 to 24. The R.sub.1 substituent may also be another --CR.sub.2
R.sub.3 C.tbd.N, and again R.sub.2 and R.sub.3 are each H, a C.sub.1-24
alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or
alkoxylated alcohol where the alkoxy unit is C.sub.2-4, and illustrative
such groups are:
##STR7##
where j=1 to 24.
Formula IB illustrates dimeric embodiments of the invention where R.sub.4
is a linking group. This linking group R.sub.4 may be a polyoxyalkylene
group with 1 to 24 oxyalkylene units, such as groups derived from ethylene
oxide, propylene oxide, butylene oxide, or mixtures thereof. Examples are:
##STR8##
where k=1 to 24. Thioethers may also be used. The R.sub.4 linking group
may also be an alkylene group with 1 to 24 carbons. R.sub.2 and R.sub.3
are each H, a C.sub.1-24 alkyl, cycloalkyl, or alkaryl, or a repeating or
nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is
C.sub.2-4. R.sub.2 ' and R.sub.3 ' chosen from the same moieties as
R.sub.2 and R.sub.3 and which may be the same as R.sub.2 and R.sub.3 or be
different.
Particularly preferred, saturated rings forming the cyclic configuration A
of Formula I contain six atoms including the N.sub.1 atom, but the number
of atoms forming the cyclic configuration can range from 3 to 9. when two
heteroatoms are present with the cyclic configuration A of Formula I, then
a three member ring is unusual; but, for the cyclic configuration B of
Formula III shown below, where there may only be N.sub.1 as the sole
heteroatom, then three membered rings are very likely.
Particularly preferred activator embodiments are illustrated by Formula II
(where "Y" is at least one counterion and "n" is 0 to 23.
##STR9##
Compounds of the invention must have a saturated ring formed by the A or B
atoms and the N.sub.1 atom, since presence of an aromatic (unsaturated)
ring has been found to cause undesirable fabric yellowing when the
activators are combined with a source of active oxygen and used in
bleaching applications.
Where the saturated ring A of the Formula I structure includes two N,
atoms, and then the second N atom, designated N.sub.2, may be a secondary
amine, a tertiary amine (having the substituent --CR.sub.5 R.sub.6 CN) or
a quaternary amine (having the substituents --R.sub.2 and --CR.sub.5
R.sub.6 CN), wherein R.sub.5 and R.sub.6 may each be a hydrogen or a
C.sub.1-6 alkyl.
Novel derivatives of the invention include peroxyimidic intermediates that
are believed formed from the novel nitriles in the presence of a peroxygen
source. So formed, peroxyimidic derivatives typically would be short-lived
intermediates formed in situ when the nitriles of the invention interact
with a source of hydrogen peroxide and where the reactive nitrile moiety
forms a peroxyimidic acid. However, such peroxyimidic derivatives may also
be prepared in isolatable, stable form by analogy to syntheses known in
the art.
COUNTERIONS
Since compounds of the invention are typically quaternized, they will
include at least one counterion (designated as "Y"), which can be
substantially any organic or inorganic anion, such as, but not limited to,
chloride, bromide, nitrate, alkyl sulfate, and the like. Dimeric
activators (e.g. Formula IB) will include at least two counterions, or a
doubly charged anion, such as sulfate, carbonate, and the like.
BLEACHING AND CLEANING COMPOSITIONS
Bleaching and cleaning compositions of the invention include a nitrile as
activator, together with a source of active oxygen. The nitrile activator
of inventive compositions is represented by Formula III (A and B).
##STR10##
In Formula III, B is a saturated ring formed by a plurality of atoms in
addition to the N.sub.1 atom, and the ring atoms preferably include at
least one carbon atom and at least one of O, S and N atoms, but can be
composed of the one N.sub.1 atom and the rest carbons. The R.sub.1,
R.sub.2, R.sub.3, R.sub.2 ', R.sub.3 ', R.sub.4, R.sub.5, and R.sub.6
groups and the Y counterion are as previously described.
Most of the compounds having the Formula III structure are novel. In
addition, compounds, for example, a N-methyl piperidinium acetonitrile
salt, which is included in the Formula III structure, when combined with a
source of active oxygen, constitute novel bleaching compositions.
Compounds having the Formula I and Formula III structures have a saturated
ring formed by a plurality of atoms, broadly ranging from 3 to 9, although
preferably containing 6 atoms including the N.sub.1 atom. Preparation of
these compounds will most conveniently start with a compound already
having the formed ring. For example, a number of preparations of inventive
nitriles hereinafter described will begin with morpholine (see, e.g., the
Formula II structure). An example of three membered rings is aziridine,
e.g., N-methylacetonitrile aziridinium; as an example of four membered
rings there is azetidine, e.g., N-ethylacetonitrile azetidinium; as an
example of five membered rings there is pyrrolidine, e.g.,
N-butylacetonitrile pyrrolidinium; as an example of six membered rings, in
addition to morpholine, there is piperidine, e.g., N-methylacetonitrile
piperidinium; as an example of seven membered rings there is
homopiperidine, e.g., N-ethylacetonitrile homopiperidinium; as an example
of eight membered rings there is tropane, e.g.,
N-methylacetonitrile-8-azabicyclo›3.2.1!octane; and, as an example of nine
membered rings there is octahydroindole, e.g., N-methylacetonitrile
octahydroindolinium.
The peroxide or active oxygen source for compositions of the invention may
be selected from the alkaline metal salts and alkaline earth metal salts
of percarbonate, perborate, persilicate and hydrogen peroxide adducts and
hydrogen peroxide. Most preferred are sodium percarbonate, sodium
perborate mono- and tetrahydrate, and hydrogen peroxide. Other peroxygen
sources may be possible, such as monopersulfates and monoperphosphates. In
liquid applications, liquid hydrogen peroxide solutions are preferred, but
the activator may need to be kept separate therefrom prior to combination
in aqueous solution to prevent premature decomposition.
The range of peroxide to activator is preferably determined as a molar
ratio of peroxide to activator. Thus, the range of peroxide to each
activator is a molar ratio of from about 0.1:1 to 100:1, more preferably
about 1:1 to 10:1 and most preferably about 2:1 to 8:1. This peracid
activator/peroxide composition should provide about 0.5 to 100 ppm A.O.,
more preferably about 1 to 50 ppm peracid A.O. (active oxygen), and most
preferably about 1 to 20 ppm peracid A.O., in aqueous media for typical
laundry applications. Formulations intended for hard surface cleaning will
more typically have peracid activator/peroxide providing from about 0.5 to
1,000 ppm A.O., more preferably about 1 to 500 ppm peracid A.O., and most
preferably about 1 to 200 ppm peracid A.O.
Compositions of the invention have been found to provide superior bleaching
(cleaning and stain removal) benefits on common laundry stains when
compared to a prior known activator containing an aromatic ring
(N-acetonitrile pyridinium chloride). Thus, Table 1 summarizes comparative
data between two different compositions of the invention compared with the
prior art, N-acetonitrile pyridinium chloride activator together with a
source of active oxygen.
The experiment summarized by the data of Table 1 is more fully described by
Example 5.
TABLE 1
______________________________________
% Stain Removal, 8-
Stain Average
______________________________________
Inventive Compositions
MMA Activator 72.4
BMA Activator 73.6
Prior Art Composition
PYACN Activator 63.2
______________________________________
The "MMA" activator was the novel Nmethyl morpholinium acetonitrile methy
sulfate, the novel "BMA" activator was Nbutyl morpholinium acetonitrile
chloride, and the prior art activator "PYACN" was Nacetonitrile pyridiniu
chloride. All three bleaching compositions included peroxide (in addition
to the particular activator) supplied in the form of hydrogen peroxide by
adding 0.11 milliliters of 30% stock to 1.5 liter wash volumes to give th
equivalent of 25 pp
The inventive compositions provide a substantial brightness (whiteness
improvement due to bleaching) and whitening (lack of colored byproduct
formation) benefits following washing. A comparison of some inventive
advantages over a composition with another prior art activator is
summarized by the data of Table 2.
TABLE 2
______________________________________
Whiteness
Fluorescence
(Unit change
(Unit change
with UV without UV
Filter) Filter)
______________________________________
Inventive
Composition
MMA Activator 1.72 2.10
Prior Art
Composition
NM4CP Activator
0.49 -0.04
______________________________________
The MMA activator was the inventive Nmethyl morpholinium acetonitrile
methyl sulfate. The prior art "NM4CP" activator was
Nmethyl-4-cyanopyridinium methyl sulfate. Each composition included 20 pp
active oxygen.)
As shown by the data of Table 2 (more fully described in Example 6), the
inventive composition provided substantial whiteness and whitening by
comparison to a prior art composition which caused unacceptable fabric
yellowing. The novel composition delivered its brightening and whitening
benefit without negatively affecting fluorescent whitening agents.
DELIVERY SYSTEMS
The activators can be incorporated into a liquid or solid matrix for use in
liquid or solid detergent bleaches by dissolving into an appropriate
solvent or surfactant or by dispersing onto a substrate material, such as
an inert salt (e.g., NaCl, Na.sub.2 SO.sub.4) or other solid substrate,
such as zeolites, sodium borate, or molecular sieves. Thus, activators of
the invention can be dispersed onto a solid or granulated carrier such as
silica, clay, zeolite, polymer, hydrogel, starch, or ion exchange
material. Alternatively, solid activator can be encapsulated such as into
waxes or polymers.
Surfactants with which the activators and active oxygen compositions may be
combined or admixed include linear ethoxylated alcohols, such as those
sold by Shell Chemical Company under the brand name Neodol. Other suitable
nonionic surfactants can include other linear ethoxylated alcohols with an
average length of 6 to 16 carbon atoms and averaging about 2 to 20 moles
of ethylene oxide per mole of alcohol; linear and branched, primary and
secondary ethoxylated, propoxylated alcohols with an average length of
about 6 to 16 carbon atoms and averaging 0-10 moles of ethylene oxide and
about 1 to 10 moles of propylene oxide per mole of alcohol; linear and
branched alkylphenoxy (polyethoxy) alcohols, otherwise known as
ethoxylated alkylphenols, with an average chain length of 8 to 16 carbon
atoms and averaging 1.5 to 30 moles of ethylene oxide per mole of alcohol;
and mixtures thereof.
Further suitable nonionic surfactants may include polyoxyethylene
carboxylic acid esters, fatty acid glycerol esters, fatty acid and
ethoxylated fatty acid alkanolamides, certain block copolymers of
propylene oxide and ethylene oxide, and block polymers or propylene oxide
and ethylene oxide with propoxylated ethylene diamine. Also included are
such semi-polar nonionic surfactants like amine oxides, phosphine oxides,
sulfoxides and their ethoxylated derivatives.
Anionic surfactants may also be suitable. Examples of such anionic
surfactants may include the ammonium, substituted ammonium (e.g.,
mono-di-, and triethanolammonium), alkali metal and alkaline earth metal
salts of C.sub.6 -C.sub.20 fatty acids and rosin acids, linear and
branched alkyl benzene sulfonates, alkyl sulfates, alkyl ether sulfates,
alkane sulfonates, alpha olefin sulfonates, hydroxyalkane sulfonates,
fatty acid mono glyceride sulfates, alkyl glyceryl ether sulfates, acyl
sarcosinates and acyl N-methyltaurides.
Suitable cationic surfactants may include the quaternary ammonium compounds
in which typically one of the groups linked to the nitrogen atom is a
C.sub.12 -C.sub.18 alkyl group and the other three groups are short
chained alkyl groups which may bear inert substituents such as phenyl
groups.
Suitable amphoteric and zwitterionic surfactants containing an anionic
water-solubilizing group, a cationic group or a hydrophobic organic group
include amino carboxylic acids and their salts, amino dicarboxylic acids
and their salts, alkyl-betaines, alkyl aminopropylbetaines, sulfobetaines,
alkyl imidazolinium derivatives, certain quaternary ammonium compounds,
certain quaternary phosphonium compounds and certain tertiary sulfonium
compounds.
Other common detergent adjuncts may be added if a bleach or detergent
bleach product is desired. If, for example, a dry bleaching and cleaning
composition is desired, the following ranges (weight %) appear
practicable:
______________________________________
0.5-50.0% Active Oxygen Source
0.05-25.0% Activator
1.0-50.0% Surfactant
1.0-50.0% Buffer
5.0-99.9% Filler, stabilizers, dyes,
fragrances, brighteners, etc.
______________________________________
An example of a practical execution of a liquid delivery system is to
dispense separately metered amounts of the activator (in some non-reactive
fluid medium) and liquid hydrogen peroxide in a container such as
described in Beacham et al., U.S. Pat. No. 4,585,150, issued Apr. 29,
1986. Such a dual bottle is contemplated for applications such as hard
surface cleaners. It should also be understood that liquid formulations of
the invention can have activator and a source of active oxygen present
together so long as the pH of the solution is maintained in an acidic
region, preferably between pH 0 and 4. Such a liquid formulation is
storage stable. In order for activation to occur during use, such a liquid
formulation will have the solution in or changed to an alkaline range,
preferably a pH of about 8 to 11, and most preferably a pH of 9.5 to 11.
In laundry use, this can automatically be achieved by adding such a liquid
formulation to the wash, with activation occurring due to the presence of
detergent as a source of alkalinity.
To summarize the single container and dual container delivery embodiments,
a single container may include acetonitrile activator, surfactant, active
oxygen source, and an acidic buffer (in order to stabilize the
acetonitrile activator and the oxygen source (if hydrogen peroxide)). The
liquid in which the just described components will be dispersed will
sometimes be referred to as a "liquid matrix." This liquid matrix will
include liquid (typically water) and remaining desired components such as
whiteners, fragrances, colorants, stabilizers, preservatives, ionic
strength adjuster, and the like. In a dual delivery embodiment, there may
be one chamber containing the just described single container composition
while the other chamber holds an alkaline solution. These two liquids
could be combined in a third, mixing chamber of a trigger sprayer or other
dispenser, or could be co-delivered to a selected site, for example, as
two directed fluid streams (via a pump or trigger sprayer device) to a
stain on a fabric, as in a "prewash" execution, or a stain on a hard
surface. In another second dual delivery embodiment, it is the source of
active oxygen that is contained in a second container until the two are
combined for use. A third dual delivery embodiment can have the source of
active oxygen and alkaline buffer in the one container and the
acetonitrile activator, surfactant, and liquid matrix in the other. Other
multiple delivery options are possible.
Compositions of the invention, when combined with a source of active
oxygen, preferably function for bleaching best at an alkaline pH, but are
shelf-stabilized best at an acidic pH. Thus, compositions of the invention
preferably include buffer (admixed or in a separate container) which will
either be acidic, alkaline, or both, depending upon whether the delivery
system is single or double. In selecting a buffer to provide an acidic pH,
a mineral acid such as HCl sulfuric, nitric, phosphoric, sulfonic, methyl
sulfuric, or organic such as citric, oxalic, glutaric, acetic, benzene
sulfonic, etc., are Well known to the art. The alkaline buffer may be
selected from sodium carbonate, sodium bicarbonate, sodium borate, sodium
silicate, phosphoric acid salts, and other alkali metal/alkaline earth
metal salts known to those skilled in the art. Organic buffers, such as
succinates, maleates and acetates may also be suitable for use. When the
composition is ready for use, it is especially advantageous to have an
amount of alkaline buffer sufficient to maintain a pH greater than about
8, more preferably in the range of about 8.5 to about 10.5 for most
effective bleaching.
Compositions of the invention will typically include a filler material,
which in solid (e.g. granulated) compositions of the invention can be
viewed as forming all or part of a matrix where the nitrile is carried by
or encapsulated in the solid matrix. The filler material (which may
actually constitute the major constituent by weight) is usually sodium
sulfate. Sodium chloride is another potential filler.
Other adjuncts (useful in cleaning and laundering applications) are
optionally included in the inventive compositions. Dyes include
anthraquinone and similar blue dyes. Pigments, such as ultramarine blue
(UMB), may also be used, and can have a bluing effect by depositing on
fabrics washed with a detergent bleach containing UMB. Monastral colorants
are also possible for inclusion. Brighteners or whiteners, such as
stilbene, styrene and styrylnaphthalene brighteners (fluorescent whitening
agents), may be included. Fragrances used for aesthetic purposes are
commercially available from Norda, International Flavors and Fragrances
and Givaudon. Stabilizers include hydrated salts, such as magnesium
sulfate, and boric acid.
In some of the compositions herein, adjuvants include (and are especially
preferred) a chelating agent or sequestrant, most preferably, an
aminopolyphosphonate. These chelating agents assist in maintaining the
solution stability of the activators and active oxygen source in order to
achieve optimum performance. In this manner, they are acting to chelate
heavy metal ions, which cause catalyzed decomposition of the (believed) in
situ formed peroxyimidic acids, although this is a non-binding theory of
their action and not limiting.
The chelating agent is selected from a number of known agents which are
effective at chelating heavy metal ions. The chelating agent should be
resistant to hydrolysis and rapid oxidation by oxidants. Preferably, it
should have an acid dissociation constant (pK.sub.a) of about 1-9,
indicating that it dissociates at low pH's to enhance binding to metal
cations. Acceptable amounts of the (optional) chelating agent range from
0-1,000, more preferably 5-500, most preferably 10-100 ppm chelating
agent, in the wash liquor.
The most preferred chelating agent is an aminopolyphosphonate, which is
commercially available under the trademark Dequest from Monsanto Company.
Examples thereof are Dequest 2000, 2041, and 2060. (See also Bossu U.S.
Pat. No. 4,473,507, column 12, line 63 through column 13, line 22,
incorporated herein by reference.) A polyphosphonate, such as Dequest
2010, is also suitable for use.
Other chelating agents, such as ethylenediaminetetraacetic acid (EDTA) and
nitrilotriacetic acid (NTA) may also be suitable for use. Still other new,
preferred chelating agents are new propylenediaminetetraacetates, such as
Hampshire 1,3 PDTA, from W. R. Grace, and Chel DTPA 100#F, from Ciba-Geigy
A. G. Mixtures of the foregoing may be suitable.
Additional desirable adjuncts are enzymes (although it may be preferred to
also include an enzyme stabilizer). Proteases are one especially preferred
class of enzymes. They are preferably selected from alkaline proteases.
The term "alkaline," refers to the pH at which the enzymes'activity is
optimal. Alkaline proteases are available from a wide variety of sources,
and are typically produced from various microorganism (e.g., Bacillus
subtilisis). Typical examples of alkaline proteases include Maxatase and
Maxacal from International BioSynthetics, Alcalase, Savinase, and
Esperase, all available from Novo Industri A/S. See also Stanislowski et
al., U.S. Pat. No. 4,511,490, incorporated herein by reference.
Further suitable enzymes are amylases, which are carbohydrate-hydrolyzing
enzymes. It is also preferred to include mixtures of amylases and
proteases. Suitable amylases include Rapidase, from Societe Rapidase,
Milezyme from miles Laboratory, and Maxamyl from International
BioSynthetics.
Still other suitable enzymes are cellulases, such as those described in
Tai, U.S. Pat. No. 4,479,881, Murata et al., U.S. Pat. No. 4,443,355,
Barbesgaard et al., U.S. Pat. No. 4,435,307, and Ohya et al., U.S. Pat.
No. 3,983,082, incorporated herein by reference.
Yet other suitable enzymes are lipases, such as those described in Silver,
U.S. Pat. No. 3,950,277, and Thom et al., U.S. Pat. No. 4,707,291,
incorporated herein by reference.
The hydrolytic enzyme should be present in an amount of about 0.01-5% ,
more preferably about 0.01-3% , and most preferably about 0.1-2% by weight
of the detergent. Mixtures of any of the foregoing hydrolases are
desirable, especially protease/amylase blends.
Anti-redeposition agents, such as carboxymethylcellulose, are potentially
desirable. Foam boosters, such as appropriate anionic surfactants, may be
appropriate for inclusion herein. Also, in the case of excess foaming
resulting from the use of certain surfactants, anti-foaming agents, such
as alkylated polysiloxanes, e.g. dimethylpolysiloxane, would be desirable.
APPLICATIONS
Compositions of the invention are useful as or in laundry products, such as
bleaching additives, detergents, detergent boosters, detergents with
bleach, bleaches, bleaching aids, stain removers, and spot treatment
products such as stain removers, prewash and presoak laundry aids. Among
the advantages derived from compositions of the invention are improved
cleaning, stain removal, spot removal, whitening, and brightening of
treated articles.
Further benefits from use of the inventive compositions include scavenging
of free dye during laundering to prevent dye transfer between garments
(sometimes known as dye transfer inhibition).
Other product applications include household cleaning products, such as
hard surface cleaners either for direct use or to be diluted with water
prior to use. Exemplary surface cleaners are tile and grout cleaners,
bathroom (floor, toilet, and counter) and kitchen (floor, sink, and
counter) cleaners. Additionally, kitchen products such as dishwasher
detergents with bleach or bleach cleaning and scrubbing pads are
contemplated. Among the benefits derived from use of the inventive
compositions in such applications are improved stain and spot removal and
general cleaning of the treated surfaces to remove food, rust, grime,
mildew, mold, and other typical stains found on such surfaces.
Additionally, non-household product applications are contemplated where an
effective level of active oxygen generated in situ to treat water is
useful. Illustrative of such applications are pool and spa additives, as
well as cleaners to remove stains on outdoor concrete, stucco, siding,
wood and plastic surfaces.
Aspects of the invention will now be illustrated by the following examples.
Example 1 (with subparts 1A-1D) illustrates preparation of embodiments
having Formula II structures. Example 2 (with subparts 2A and 2B)
illustrates preparation of embodiments having the Formula IB structure.
Examples 3-7 illustrate various aspects and properties of the invention.
It will be understood that these examples are intended to illustrate, and
not to limit, the invention.
EXAMPLE 1
In general, N-quaternary acetonitrile compounds are readily prepared from
N-acetonitrile precursors by employing selected alkyl halides and using
well-known synthetic approaches, such as are described by Menschutkin, Z.
Physik. Chem., 5, 589 (1890), and Z. Physik. Chem., 6, 41 (1890); Abraham,
Progr. Phys. Org. Chem., 11, 1 (1974); and Arnett, J. Am. Chem. Soc., 102,
5892 (1980).
Specifically detailed preparations of four preferred embodiments are
described below as illustrative.
EXAMPLE 1A
Preparation of N-Methyl Morpholinium Acetonitrile (MMA)
To a solution of 30 g of morpholine acetonitrile in 75 ml of ethyl acetate
was added 22.5 ml of dimethyl sulfate, corresponding to approximately
equivalent molar amounts of the two reagents. The resulting solution was
mechanically stirred in an oil bath maintained at 40.degree. C. After 10
minutes of stirring, a semi-solid precipitate having a brownish coloration
formed and settled on the bottom of the flask. HPLC (high pressure liquid
chromatography) analysis showed at least 4 undesirable side products,
which were removed. The remaining solution was again heated to 40.degree.
C. and reacted for an additional 16 hours. After this time, the resulting
white paste was filtered and washed with ethyl acetate. MMA was isolated
after drying this filtrate as a free flowing off-white solid in 79% yield,
having a melting point of 99.degree.-101.degree. C. The purity of the MMA
was determined by HPLC to be greater than 95%.
EXAMPLE 1B
Preparation of N-Hexyl Morpholinium Acetonitrile (HMA)
Combined were 44.08 g of hexylbromide, 29.88 g morpholine, and 28.0 g
anhydrous sodium carbonate with 150 ml of acetone in a large round bottom
flask. This mixture was refluxed for 8 hours at the boiling point of
acetone or approximately 60.degree. C., then cooled to room temperature
and the solid sodium carbonate filtered. Acetone was removed using a
roto-evaporator. The resulting oil was dissolved in ether and washed twice
with water and once with brine solution. The ether solution was dried over
anhydrous sodium sulfate. After filtering, ether was removed in-vacuo
leaving 45.2 g of a lightly-colored oil in 98.8% yield. Gas chromatography
showed the oil to be N-hexyl morpholine in approximately 95% purity.
Combined were 2.0 g of N-hexylmorpholine with 0.95 g of chloroacetonitrile
in a small vial. After capping the vial was heated to 55.degree. C. for
approximately 24 hours. A viscous oil resulted which solidified upon
addition of a small amount of ethylacetate. The solid was filtered and
washed with excess ethylacetate, then dried in a vacuum dessicator
resulting in 2.3 g of final white solid, in a yield of approximately 84% .
Carbon-13 NMR analysis revealed the desired product present with no other
detectable impurities noted.
EXAMPLE 1C
Preparation of N-Octyl Morpholinium Acetonitrile (OMA)
Combined were 51.5 g of octylbromide, 29.88 g morpholine, and 28.0 g
anhydrous sodium carbonate with 150 ml of acetone in a large round bottom
flask. This mixture was refluxed for 8 hours at the boiling point of
acetone or approximately 60.degree. C., then cooled to room temperature
and the solid sodium carbonate filtered. Acetone was removed using a
roto-evaporator. The resulting oil was dissolved in ether and washed twice
with water and once with brine solution. The ether solution was dried over
anhydrous sodium sulfate. After filtering, ether was removed in-vacuo,
leaving a slightly-colored oil. Gas chromatography showed the oil to be
N-octyl morpholine, obtained with a yield of 98% and having greater than
95% purity. Combined were 2.3 g of N-octyl morpholine together with 1.0 g
of chloroacetonitrile in a small vial. After capping the vial was heated
to 55.degree. C. for approximately 24 hours. A viscous oil resulted which
solidified upon addition of a small amount of ethylacetate. The solid was
filtered and washed with excess ethylacetate, then dried in a vacuum
dessicator resulting in the isolation of a white solid, in a yield of
approximately 84% . Carbon-13 NMR analysis revealed the desired product
present with no other detectable impurities noted.
EXAMPLE 1D
Preparation of N-Butyl Morpholinium Acetonitrile (BMA)
Combined were 10 g of butylbromide, 6.36 g morpholine, and 28.0 g anhydrous
sodium carbonate with 150 ml of acetone in a large round bottom flask.
This mixture was refluxed for 8 hours at the boiling point of acetone or
approximately 60.degree. C., then cooled to room temperature and the solid
sodium carbonate filtered. Acetone was removed using a roto-evaporator.
The resulting oil was dissolved in ether and washed twice with water and
once with brine solution. The ether solution was dried over anhydrous
sodium sulfate. After filtering, ether was removed in-vacuo leaving 5.15 g
of product estimated at 49.3% yield. Gas chromatography showed the product
to be N-butyl morpholine in approximately 95% purity. Combined 7.2 g of
N-butyl morpholine together with 3.0 ml of chloroacetonitrile in a small
vial. After capping the vial was heated to 60.degree. C. for approximately
24 hours. An oil resulted which solidified upon addition of a small amount
of ethylacetate. The solid was filtered and washed with excess
ethylacetate, then dried in a vacuum dessicator resulting in a white solid
in nearly stoichiometric yield. Carbon-13 NMR analysis revealed the
desired product present with no other detectable impurities noted.
EXAMPLE 2
Dimer embodiments of the invention, for example such as illustrated by
Formula IB, may be prepared as follows.
EXAMPLE 2A
1,6-Bis(4-cyanomethylmorpholinium)hexane Dichloride (HDMMA)
100 ml of morpholine (1.147 mole) and 150 ml ethylacetate (EtOAc) were
added to 500 ml Morton flask equipped with reflux condenser, thermometer,
mechanical stirrer, and heating mantel. 25 ml of 1,6-dichloro-hexane
(0,172 mole) was added slowly to flask at room temperature. This was
refluxed for 48 hours. Gas chromatogram showed 90% completion of the
reaction. The product 1,6-bismorpholinohexane was purified from reaction
mixture by vacuum filtration to remove the morpholine hydrochloride, and
the light yellow filtrate was purified by adsorption chromatography.
.sup.13 C NMR showed a spectrum consistent with structure with very minor
impurities. Gas chromatography showed an approximate purity of 98.2% based
upon peak areas. The collected amount of 1,6-bismorpholinehexane was 30.0
g, which corresponds to a yield of 66.6% .
12.68 g of bismorpholinohexane (0.049 mole) and 55 ml EtOAc were added to
500 ml Morton flask equipped with reflux condenser, pressure equalizing
dropping funnel, mechanical stirrer, and heating mantel. 15 ml of
chloroacetonitrile (0.238 mole) was added slowly to flask at room
temperature. This was refluxed for 5 hours. Light brown solid precipitated
from the solution, and the solid was isolated by vacuum filtration, rinsed
with EtOAc, and dried overnight in vacuum oven at ambient temperature.
.sup.13 C NMR showed a spectrum consistent with structure with a
significant, but small impurity of starting amine. Collected 12.6 g of
product, corresponding to 57.1% yield from this step.
EXAMPLE 2B
1,2-Bis (2-(4-cyanomethylmorpholinium)ethoxy)ethane Dichloride (EODMMA)
100 ml of morpholine (1.147 mole) and 150 ml EtOAc were added to 500 ml
Morton flask equipped with reflux condenser, thermometer, mechanical
stirrer, and heating mantel. 25 ml of 1, 2-bis(2-chloroethoxy)ethane
(0.160 mole) added slowly to flask at room temperature. This was refluxed
for 16 hours. Product 1,2-bis(2-morpholinoethoxy)ethane was purified from
reaction mixture by vacuum filtration to remove the morpholine
hydrochloride, and the light yellow filtrate was purified by adsorption
chromatography. 18.4 g of product was collected, and a gas chromatogram
showed an approximate purity of 98.2% based upon peak areas. The collected
amount of 1,2-bis(2-morpholinoethoxy)ethane corresponds to a yield of
39.2%.
14.94 g of 1,2-bis(2-morpholinoethoxy)ethane (0,051 mole) and approximately
100 ml EtOAc were added to 500 ml Morton flask equipped with reflux
condenser, pressure equalizing dropping funnel, mechanical stirrer, and
heating mantel. 25 ml of chloroacetonitrile (0.397 mole) was added slowly
to flask at room temperature. This was refluxed for 8 hours. Light brown
solid precipitated from the solution, and the solid was very tacky and
stiff. The mechanical stirrer froze solid in the material. Mother liquor
was decanted off the solid, and the solid was redissolved in methanol. The
solvent was evaporated in a recrystallization dish for several days.
Mother liquor reacted further for an additional 8 hours without any
stirring, with more product forming. The product from the second heating
was collected in a manner identical to first. 14.6 g of product was
collected from the first reaction period and 5.5 g from the second
reaction period. Together the two reactions yielded 20.1 g of product,
corresponding to 85.4% yield. .sup.13 C NMR shows spectrum consistent with
the proposed structure with a small impurity of methanol.
EXAMPLE 3
Compounds with the Formula I or Formula III structure are particularly
contemplated as activators in bleaching applications. Therefore, a desired
property of these compounds is that of exhibiting perhydrolysis when
combined with hydrogen peroxide. As summarized by the data in Table 3,
titrated perhydrolysis yields with excess hydrogen peroxide present (as
determined by electrochemical analyzer with response standardized against
oxone or peroxide standard solution) were performed for six preferred
embodiments of the invention.
TABLE 3
______________________________________
Titrated
Name % Yield
______________________________________
N-Methyl Morpholinium Aceto-
46
nitrile Methyl Sulfate, (MMA)
N-Hexyl Morpholinium 55
Acetonitrile Chloride (HMA)
N-Octyl Morpholinium Aceto-
42
nitrile Chloride (OMA)
N-Methyl-piperazinium-N,N,
31.5
diacetonitrile Methyl Sulfate
(MPDA)
1,6-di(4-Cyanomethyl-
40
morpholinium)hexane Dichloride
(HDMMA)
1,2-bis(2-(4-Cyanomethyl-
20
morpholinium)ethoxy)ethane
dichloride (EODMMA)
______________________________________
We believe that the acetonitrile moiety is necessary for the perhydrolysis
activity, since a compound analogous to MMA, but with a proprionitrile
moiety instead of the acetonitrile moiety, was shown to have no
perhydrolysis yield when tested at pH 10.
Bleaching compositions of the invention include a source of active oxygen.
The source of active oxygen itself constitutes a bleaching agent; however,
bleaching compositions of the invention that include the Formula I or
Formula III nitriles as activators, together with a source of active
oxygen, provide enhanced bleaching with respect to the oxygen source by
itself. This is demonstrated by Examples 3A and 3B.
EXAMPLE 3A
In a commercial washing machine (with scoured ballast) garments were split
and washed in either of two treatments. Wash conditions were warm water
(93.degree. F.) using No-P Grease Release Tide (65 g) in a 69 L washer, 1
min. premix time with 12 minute wash, cold water (68.degree. F.) rinse
with 100 ppm hardness as Ca.sup.2+ :Mg.sup.2+ (3:1).
The two treatments were either (1) Clorox 2 Colorbright (76.2 g) delivering
18 ppm A.O. (theoretical active oxygen) as sodium perborate (7.75 g), and
a wash pH between 10.5-10.6; or (2) an inventive bleaching composition,
but additionally containing 12 ppm A.O. as MMA (13.05 g-active) and 28 ppm
A.O. as sodium perborate (12.05 g) and sodium bicarbonate substituted in
part for sodium carbonate to achieve a wash water pH between 10.0-10.1.
Both treatments also contained Dequest 2006 at an active level of 0.69 g
added in a 69 L wash volume. 40 split garment halves and socks were
visually judged in a blind side-by-side panel to compare treatment
differences, as shown by Table 4.
TABLE 4
______________________________________
Winner at 95%
Garment/
Mean Standard Confidence
Confidence
Evaluation
Score Error Level Level
______________________________________
Socks/ 0.49 0.22 96.96 Inventive
Cleaning bleaching
composition
with MMA
Dress Shirt
0.33 0.13 98.56 Inventive
Color/ bleaching
Cleaning composition
with MMA
T-Shirt/
0.53 0.19 99.00 Inventive
Whiteness bleaching
composition
with MMA
______________________________________
The mean score reported in Table 4 is the average of all judges responses
on a scale of -4 to +4, evaluating either overall cleaning or whiteness
differences between halves or matched pairs (socks).
As is demonstrated by the data of Table 4 above, the inventive bleaching
composition (with MMA as activator) showed superior bleaching to perborate
bleach alone on various soiled consumer garments.
EXAMPLE 3B
A commercial washing machine was used with scoured ballast. Wash conditions
were warm wash (98.degree. F.) using No-P Grease Release Tide (65 g) in a
69 L washing, 1 min. premix time with 12 minute wash, cold water
(68.degree. F.) rinse with 100 ppm hardness at Ca.sup.2+l :Mg.sup.2+
(3:1). Treatments included enzyme (Savinase 6T-0.83 g), whitener speckles
containing Blankophor HRS (1.71 g), metal sequestrant (Dequest 2006-1.73
g/69 L) and one of three sodium carbonate/sodium bicarbonate mixtures to
achieve desired wash water pH: pH 10.5-11.9 g NaCl and 55.6 g Na.sub.2
CO.sub.3 ; pH 10.0-40.5 g Na.sub.2 CO.sub.3 and 27 g Na.sub.2 HCO.sub.3 ;
pH 9.5-13.5 g Na.sub.2 CO.sub.3 and 54 g Na.sub.2 HCO.sub.3, all weight
added per single 69 L wash volume to maintain equivalent ionic strength.
TABLE 5
______________________________________
% Stain Removal Relative
to Wash with Control
Detergent Wash
Fountain 8-Stain
Tea Pen Ink Average
______________________________________
Inventive
Compositions
1 (pH 10.5, 4 ppm
25 23 11
MMA, 18 ppm A.O.)
2 (pH 9.5, 8 ppm
19 30 9
MMA, 18 ppm A.O.)
3 (pH 10.5, 8 ppm
25 30 10
MMA, 18 ppm A.O.)
4 (pH 10.0, 8 ppm
27 32 9
MMA, 18 ppm A.O.)
5 (pH 10.5, 12 ppm
31 33 14
MMA, 28 ppm A.O.)
6 (pH 10.5, 16 ppm
38 37 16
MMA, 36 ppm A.O.)
Comparative
Composition
(pH 10.5, 18 ppm
15 1 6
A.O.)
______________________________________
As is shown by the data of Table 5 above, six compositions of the invention
(with the inventive MMA activator) performed substantially better in
removing tea stains than the comparative perborate, and removed fountain
pen ink stain 20 to almost 40 times better than the perborate. Over an
eight stain average (including grass, coffee, tea, gravy, grape,
spaghetti, berry, and mustard) the inventive bleaching compositions were
consistently better than the comparative perborate at bleaching. The data
are differences in stain removal versus the no-P Tide wash.
EXAMPLE 4
This example illustrates the substantial bleaching (cleaning and stain
removal) benefits on common laundry stains of several different inventive
compositions when used as a laundry additive with respect to use of
detergent alone and with respect to use of the detergent plus hydrogen
peroxide source alone.
Single 12 minute washes in No-P Ultra Tide detergent (0.95 g/L) at
98.degree. F. were followed by a 1 minute cold water rinse. All washes
contained 100 ppm hardness ions (Ca.sup.2+ :Mg.sup.2+ at 3:1), sodium
bicarbonate/sodium carbonate mixture (0.364 g/L and 0.545 g/L,
respectively) to adjust wash water to approximately pH 10, and Dequest
2006 at 0.026 g/L. Wash volume was 1.5 liters with agitation at 150 ppm
using a six-well Terg-o-tometer. Stains were made on 100% cotton using
common food and stain ingredients: coffee, tea, grape, berry, ball point
pen ink (BPI) and fountain pen ink (FPI). One standard stained flag
containing all stains and six clean cotton swatches for ballast were
washed per well. Stain removal was measured photometrically by determining
delta SR(e) from colorimeter readings before and after washing. Level of
oxidant is theoretical % active oxygen in ppm (ppm A.O.) based on formula
weight and number of equivalents. Peroxide (H.sub.2 O.sub.2) was supplied
in the form of sodium perborate monohydrate, where 0.156 g/L corresponds
to 25 ppm active oxygen (AO) in the Terg-o-tometer.
TABLE 6
______________________________________
% S.R.
Fountain 6-Stain
Tea Grape Pen Ink Average
______________________________________
Inventive Compositions:
7 (10 ppm MMA, 25 ppm
47.7 84.1 83.2 79.1
A.0.)
8 (10 ppm HMA, 25 ppm
37.4 81.6 78.9 76.8
A.0.)
9 (10 ppm OMA, 25 ppm
34.4 81.3 75.5 75.6
A.0.)
10 (10 ppm MPPA, 25 ppm
41.9 84.8 82.9 78.6
A.0.)
11 (10 ppm MPA*, 25 ppm
42.9 80.0 80.8 77.0
A.0.)
Control Compositions:
Detergent only
31.4 63.4 52.1 61.1
Peroxide and 32.5 64.9 51.0 63.2
Detergent (25 ppm
A.0.)
______________________________________
*N-methyl piperidinium acetonitrile methyl sulfate
As seen by the data of Table 6 above, all the inventive compositions
provided improved cleaning and stain removal with respect to the detergent
only control composition and with respect to the peroxide and detergent
control composition.
EXAMPLE 5
This example again demonstrates the excellent bleaching (cleaning and stain
removal) benefit of inventive compositions and also serves to compare two
of the inventive embodiments with a prior art composition where the
nitrile activator has an aromatic ring. This prior art bleaching
composition is N-acetonitrile pyridinium chloride ("PYACN") as the
activator.
All treatments were duplicated 12 minutes in No-P Ultra Tide detergent with
Cellulase (1.53 g/1.5 L) at 96.degree. F., followed by 1 minute cold water
rinse. All washes contained 100 ppm hardness (Ca.sup.2+ :Mg.sup.2+ at
3:1). Wash volume was 1.5 liters with agitation at 150 ppm using a
six-well Terg-o-tometer. Stains were made using a SAM (Stain Application
Machine) on 100% cotton using common food stain ingredients: grass,
coffee, tea, grape, spaghetti, mustard, berry, and fountain pen ink (FPI).
Two standard stained flags containing all stains and six clean cotton
swatches for ballast were washed per well. Stain removal was measured
photometrically by determining delta SR(e) from colorimeter readings
before and after washing. Level of oxidant was theoretical % active oxygen
in ppm (ppm A.O.) based on formula weight and number of equivalents.
Peroxide (H.sub.2 O.sub.2) was supplied in the form of hydrogen peroxide
by adding 0.11 ml of 30% stock to 1.5 L wash volumes to give the
equivalent of 25 ppm active oxygen (AO) in the Terg-o-tometer.
TABLE 7
______________________________________
% S.R.
Fountain 8-Stain
Tea Grape Pen Ink Average
______________________________________
Inventive Compositions:
12 (12 ppm MMA, 25 ppm
54.6 73.4 80.2 72.4
A.0.)
13 (12 ppm BMA, 25 ppm
51.2 76.4 77.1 73.6
A.0.)
Comparative Composition
(12 ppm PYACN, 25
42.0 65.2 63.1 63.2
ppm A.0.)
Control Compositions
Detergent only
34.8 54.8 49.7 65.9
Detergent and 25 ppm
39.6 57.9 51.9 67.1
A.0.
______________________________________
As shown by the Table 7 data above, both inventive composition embodiments
clearly outperformed the comparative bleaching composition.
EXAMPLE 6
These studies were conducted to determine whether embodiments of the
invention would deliver their brightening and whitening benefit without
negatively affecting fluorescent whitening agents that may already be
present on clothing or be present simultaneously in the wash water during
use. The "FWA" source was that present in the detergent used, or existing
on the prebrightened cotton fabric obtained from Testfabrics, Inc. The
wash study experiments also compared a prior art nitrile precursor (but
with an aromatic ring) as to brightening (whiteness improvement due to
bleaching) and whitening (lack of colored by-product formation). The prior
art activator used for comparison was N-methyl-4-cyanopyridinium
methylsulfate ("NM4CP").
All treatments contained No-P Tide (65.3 g/69 L), standard hardness (100
ppm of Ca.sup.2+ :Mg.sup.2+), sodium bicarbonate (7.2 g) to adjust
incoming wash water pH and an additional 20 g of sodium bicarbonate and 49
g of sodium carbonate to adjust final wash water pH to approximately 10.
In addition, 1.73 g of Dequest 2006 and 9.36 g of sodium perborate
monohydrate were added per 69 L. All treatments were done in conventional
washing machines using a 12 minute wash cycle. Two prebrightened cotton
T-shirt swatches were attached to pillowcases and added to each washing
machine in combination with 6 lbs. of clean ballast.
TABLE 8
______________________________________
Fluorescence
with UV
Whiteness
Filter
(Unit Change)
(Unit Change)
______________________________________
Inventive Composition:
14 (8 ppm MMA, 20 ppm
3.82 2.10
A.0.)
Comparative Composition:
(8 ppm NM4CP, 20 ppm
0.45 -0.04
A.0.)
Control Compositions:
Detergent only 2.63 1.57
Detergent and 20 ppm
2.84 1.69
A.0.
______________________________________
As shown by the data of Table 8 above, the inventive composition embodiment
delivered its brightening and whitening benefit without negatively
affecting the FWAs. By contrast, the comparative bleaching composition
negatively affected the FWAs and caused unacceptable fabric yellowing,
perhaps due to reactions pertaining to the aromatic ring of the prior art
nitrile activator.
EXAMPLE 7
Four granulated compositions of the invention were formulated and tested
for storage stability. Table A sets out the formulations, and Table 9B
summarizes the percent remaining perhydrolysis activity after six weeks at
80% F storage (80% relatively humidity).
TABLE 9A
______________________________________
Inventive Composition No.
15 16 17 18
Component Wt. % Wt. % Wt. % Wt. %
______________________________________
Activator (MMA)
13.7 6.8 6.9 20.4
Active Oxygen
8.8 9.2 9.2 7.8
Source (Sodium
Perborate Hydrate)
Buffer/(Sodium
71.0 74.5 74.5 63.3
Carbonate) Filler
Builder 1.2 1.3 1.3 1.1
(Polyacrylate)
Chelating 0.8 0.8 0.8 0.7
Agent/Sequestrant
Filler/(Sodium
3.0 3.2 3.2 2.7
Silicate) Buffer
Enzyme 0 0.9 0.9 0.9
Miscellaneous
1.5 3.3 3.2 3.1
(color, whitener,
etc.)
______________________________________
TABLE 9B
______________________________________
Inventive Composition
% Wt. Active MMA
Number remaining
______________________________________
15 100
16 74
17 100
18 86
______________________________________
As shown by the data of Table 9B, the inventive composition embodiments
exhibited good storage stability.
It is to be understood that while the invention has been described above in
conjunction with preferred specific embodiments, the description and
examples are intended to illustrate and not limit the scope of the
invention, which is defined by the scope of the appended claims.
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